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The compounds (H 3 C) 2 S, (H 3 Si) 2 S and (H 3 Ge) 2 S have been crystallised in situ on a diffractometer and their crystal structures determined by low-temperature X-ray diffraction. The molecules are present as monomers in the crystals. The aggregation of the molecules through secondary intermolecular contacts in the crystal is different: (H 3 C) 2 S is weakly associated into dimers by S···S contacts, whereas (H 3 Si) 2 S and (H 3 Ge) 2 S form Si···S and Ge···S contacts in an ice-analogous aggregation motif. Important geometry parameters are (H 3 C) 2 S: C-S 1.794(av) Å , C-S-C 99.2(1)°; (H 3 Si) 2 S: Si- S 2.143(1) Å , Si-S-Si 98.4°; (H 3 Ge) 2 S Ge-S 2.223(2) and 2.230(2) Å , Ge-S-Ge 98.2(1) ◦ .

Dimethyl-, Disilyl- and Digermylsulfide: Different Intermolecular Contacts in the Solid State